JPH0940856A - Glass-reinforced polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a glass-reinforced polycarbonate resin composition having high rigidity and at the same time improved transparency. SOLUTION: This resin composition is composed of (A) 99-10 pts.wt. of a polycarbonate resin and/or a polyester carbonate resin, (B) 1-90 pts.wt. of a polyester derived from terephthalic acid and an allcyclic diol and (C) 1-60 pts.wt. of a glass filler based on the total of both the components A and B of 99-40 pts.wt. Further, the difference of the refractive index of the component A and that of the component C is <=0.01.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass-reinforced polycarbonate resin composition, and more particularly to a glass-reinforced polycarbonate resin composition having high transparency and high rigidity.

[0002]

2. Description of the Related Art Polycarbonate resins are excellent in transparency, heat resistance and impact resistance, and are therefore used as an alternative material for glass for optical applications such as lenses and prisms. However, since the rigidity is lower than that of glass, physical properties are improved by adding an appropriate filler such as glass fiber in applications requiring high rigidity.

However, when a glass filler or the like is added, there is a difference between the refractive index of glass (usually about 1.545 for conventional glass) and the refractive index of polycarbonate (usually about 1.582 for conventional polycarbonate). Since it is large, there is a disadvantage that the transparency, which is a major feature of the polycarbonate resin, is impaired.

[0004]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a glass-reinforced polycarbonate resin composition having improved transparency while maintaining high rigidity.

[0005]

The object of the present invention is to provide A) a polycarbonate resin and / or a polyester carbonate resin 99 to 10 parts by weight, and B) a polyester derived from terephthalic acid and an alicyclic diol.
1 to 90 parts by weight and a total of 99 to 40 parts by weight of both components A) and B), C) glass filler 1 to
60 parts by weight, and the difference in refractive index between the component A) polycarbonate-based resin and / or polyester carbonate-based resin and the component C) glass filler is 0.
It is solved by the glass reinforced resin composition which is 01 or less.

In the present invention, known polycarbonate resins can be used and are usually characterized as having a repeating structure of the following formula (Formula 1).

[0007]

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Here, A is a divalent aromatic residue of the polyhydric phenol used in the polymerization reaction. Dihydric phenols that can be used to obtain such aromatic polycarbonates are mono- or polynuclear aromatic compounds containing two hydroxy groups as functional groups, each of which is directly bonded to an aromatic carbon atom. It is.

There are no particular restrictions on the aromatic hydroxy compound, and known compounds of the people of the species can be used. As an example, the following formula (Formula 2)

[0010]

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In the above formula (Formula 2), R and R'are each independently a halogen atom, a monovalent hydrocarbon group or a hydrocarbon oxy group, W is a divalent hydrocarbon group, -S.
-, -S-S-, -O-, -S (= O)-,-(O =)
S (= O)-, or -C-, (= O)-, n and n'are each independently an integer of 0 to 4, and b is 0 or 1. It consists of a diphenol component derived from and a carbonate component.

In the above formula, when R and R'are halogen atoms, examples thereof include chlorine atom and bromine atom. In the case of a monovalent hydrocarbon group, an alkyl group,
Examples thereof include a cycloalkyl group, an aryl group, an aralkyl group and an alkaryl group. In the case of a hydrocarbon oxy group, examples of the hydrocarbon group include the aforementioned hydrocarbon groups.

When W is a divalent hydrocarbon group,
Alkylene group, alkylidene group, cycloalkylene group,
Or a cycloalkylidene group.

Specific examples of diphenols include diphenol; 2,2-bis (4-hydroxyphenyl) propane (so-called bisphenol A); 2,2-bis (3,5-dibromo-4-hydroxyphenyl). Propane; 2,2-bis (3,5dimethyl-4-hydroxyphenyl) propane; 1,1-bis (4-hydroxyphenyl)
Cyclohexane; 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane; 1,1-bis (4-
1,4-bis (4-hydroxyphenyl) propane; 1,1-bis (4-hydroxyphenyl) cyclododecane; 1,1-bis (3,5dimethyl-
4-hydroxyphenyl) cyclododecane; 4,4-dihydroxydiphenyl ether; 4,4-thiodiphenol; 4,4-dihydroxy-3,3-dichlorodiphenyl ether; 4,4-dihydroxy-2,5-dihydroxydiphenyl ether: and , 4,4-biphenol and the like. In addition, U.S. Pat.Nos. 2,999,835 and 3,0
The diphenols described in 28,365, 3,334,154 and 4,131,575 can be used. Such a polycarbonate can be produced, for example, by a known interfacial polymerization method using phosgene, a melt polymerization method, or the like.

In addition to the above, as the aromatic dihydroxy compound, a compound represented by the following general formula (Formula 3) can be used.

[0016]

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(Here, R ^f is each independently a carbon number of 1
It is a hydrocarbon group of 10 or its halogen compound or a halogen atom, and m is an integer of 0-4. ) Compounds such as resorcin, and 3-methylresorcin, 3-ethylresorcin, 3-propylresorcin, 3-butylresorcin, 3-t-butylresorcin, 3-phenylresorcin, 3-cumylresorcin,
2,3,4,6-Tetrafluororesorcin, 2,3,4,6-
Substituted resorcins such as tetrabrom resorcin; catechol; hydroquinone, and 3-methylhydroquinone, 3-ethylhydroquinone, 3-propylhydroquinone, 3-butylhydroquinone, 3-t-butylhydroquinone, 3-phenylhydroquinone, 3-cumyl Substituted hydroquinone such as hydroquinone, 2,3,5,6-tetrafluorohydroquinone, 2,3,5,6-tetrabromohydroquinone, and the following formula (Formula 4)

[0018]

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2,2,2 ', 2'-tetrahydro-3,3,3', 3'-tetramethyl-1,1'-spirobis (1H-indene) -7,7'-diol represented by Can also be used.

These aromatic dihydroxy compounds may be used alone or in combination of two or more.

The polycarbonate may be branched. Such a branched polycarbonate is obtained as a branched thermoplastic random branched polycarbonate by reacting a polyfunctional aromatic compound with a diphenol and / or a carbonate precursor.

The present invention further provides the following formula (Formula 5) as the component (A '):

[0023]

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And the following equation (Formula 6):

[0025]

[Chemical 6]

In the above formula, R and R'are each independently a halogen atom, a monovalent hydrocarbon group or a hydrocarbon oxy group, and W is a divalent hydrocarbon group, -S-, -S-.
S-, -O-, -S (= O)-,-(O =) S (= O)
-Or -C (= O)-, n and n'are each independently an integer of 0 to 4, and X is a carbon number of 6 to 18.
It is possible to use a copolyestercarbonate having a structural unit represented by a divalent aliphatic group having, and b is 0 or 1. Further, this copolyestercarbonate can be used together with the above-mentioned polycarbonate resin in an arbitrary ratio.

The copolyestercarbonate used in the present invention must have the structural units represented by the above formulas (Formula 5) and (Formula 6). First, the structural unit represented by (Chemical Formula 5) is composed of a diphenol component and a carbonate component. The diphenol that can be used for introducing the diphenol component is the diphenol represented by the above-mentioned chemical formula (2). In particular, in the above formula (Formula 2), when R and R'are halogen atoms, examples thereof include a chlorine atom or a bromine atom.

In the case of a monovalent hydrocarbon group, the number of carbon atoms is 1 to
An alkyl group having 12 such as a methyl group, an ethyl group,
Propyl group, decyl group, etc .; cycloalkyl group having 4 to 8 carbon atoms, such as cyclopentyl group, cyclohexyl group; aryl group having 6 to 12 carbon atoms, such as phenyl group, naphthyl group, biphenyl group, etc .; 7 carbon atoms ~ 14
An aralkyl group having, for example, a benzyl group, a cinnamyl group, or the like; or an alkaryl group having 7 to 14 carbon atoms,
Examples thereof include a tolyl group and a cumenyl group, and an alkyl group is preferable.

As the hydrocarbon group of the hydrocarbon oxy group, the above-mentioned hydrocarbon groups can be mentioned. Such a hydrocarbon oxy group is an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group or an alkaryloxy group, and an alkoxy group and an aryloxy group are preferred.

When W is a divalent hydrocarbon group,
Alkylene groups having 1 to 30 carbon atoms, such as methylene group, ethylene group, trimethylene group, octamethylene group, etc., Alkylidene groups having 2 to 30 carbon atoms, such as ethylidene group, propylidene group, etc., or 6 to 1 carbon atoms.
A cycloalkylene group having 6 such as a cyclohexylene group, a cyclododecylene group or the like or a cycloalkylidene group such as a cyclohexylidene group.

Examples of the diphenol effective in the present invention include 2,2-bis (4-hydroxyphenyl) propane (so-called bisphenol A); 2,2-bis (3,5)
-Dibromo-4-hydroxyphenyl) propane; 2,2
-Bis (3,5dimethyl-4-hydroxyphenyl) propane; 1,1-bis (4-hydroxyphenyl) cyclohexane; 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane; 1,1 -Bis (4-hydroxyphenyl) decane; 1,4bis (4-hydroxyphenyl) propane; 1,1-bis (4-hydroxyphenyl)
Cyclododecane; 1,1-bis (3,5dimethyl-4-hydroxyphenyl) cyclododecane; 4,4-dihydroxydiphenyl ether; 4,4-thiodiphenol; 4,4-
And dihydroxy-3,3-dichlorodiphenyl ether; and 4,4-dihydroxy-2,5-dihydroxydiphenyl ether, and the like, and US Pat.
999,835, 3,028,365, 3,334,154 and 4,1
The diphenols described in No. 31,575 can be used.

Further, examples of the precursor for introducing the carbonate component include phosgene and diphenyl carbonate.

Next, the constitutional unit represented by the above formula (Formula 6) comprises a diphenol component and a divalent acid component. Regarding the introduction of the diphenol component, the same diphenol as described above can be used. The monomer used to introduce the diacid component is a diacid or an equivalent thereof. The divalent acid is, for example, an aliphatic diacid having 8 to 20 carbon atoms, preferably 10 to 12 carbon atoms.

The divalent acid or its equivalent substance may be linear, branched or cyclic. The aliphatic diacid is preferably α, ω-dicarboxylic acid. As such a divalent acid, for example, straight-chain saturated aliphatic dicarboxylic acids such as sebacic acid (decandioic acid), dodecandioic acid, tetradecandioic acid, icodecandioic acid, and the like are preferable, and sebacic acid and dodecane acid are preferable. Diacids are particularly preferred.

Examples of equivalent substances include acid halides such as the above-mentioned divalent acids, such as acid chlorides, and diaromatic esters such as diphenyl esters. However, the carbon number of the ester portion of the ester is not included in the carbon number of the acid described above. The above-mentioned divalent acid or its equivalent substance may be used alone or in combination of two or more kinds.

The copolyestercarbonate of the component (A ') is the above-mentioned 2 represented by the above formulas (Formula 5) and (Formula 6).
The proportion of the constituent units of the species is arbitrary, but the unit of the formula (Formula 6) is preferably 2 mol% or more, and particularly 7 mol% or more.
When the proportion of the unit of the formula (Formula 6) is large, the refractive index of the copolyester carbonate approaches that of glass, which is preferable.

The weight average molecular weight of the component (A ') copolyestercarbonate is usually 10,000 to 100,0.
00, preferably 18,000 to 40,000.

The term "weight average molecular weight" as used herein means GPC using polystyrene corrected for polycarbonate.
(Gel permeation chromatography). (It is preferable that the inherent viscosity measured at 25 ° C. in methyl chloride is 0.35 to 0.65.)

The copolyestercarbonate as the component (A ') can be produced by a known interfacial polymerization method using phosgene, a melt polymerization method or the like. For example, Quin
nn) and U.S. Pat. No. 4,238,596 and Quinn and Markezich U.S. Pat. No. 4,238,597.

Specifically, first, an acid halide is formed prior to the reaction between the ester-forming group and diphenol, and then reacted with phosgene. Goldberg (Gol
In the basic solution method of Dberg (US Pat. No. 3,169,121), a pyridine solvent can be used and a dicarboxylic acid can be used.

Melt polymerization methods using diesters of α, ω-dicarboxylic acids (eg sebacic acid), eg diphenylesters, can also be used. A preferred method of manufacture is the improved method of Kochanowski of US Pat. No. 4,286,083. In this method, a lower diacid such as adipic acid is converted into a salt form (preferably an alkali metal salt such as a sodium salt) in advance, and is added to a reaction vessel in which diphenol is present.

During the reaction with phosgene, the aqueous phase is maintained at an alkaline pH, preferably about pH 8-9, and then at a minimum of about 5% remaining reaction with phosgene, pH 10-.
Raise to 11.

In the case of the interfacial polymerization method, for example, the bischloroformate method, it is preferable to use a general catalyst system well known in the synthesis of polycarbonate and copolyestercarbonate.

The main catalyst system includes amines such as tertiary amines, amidines or guanidines.
Tertiary amines are commonly used, of which trialkylamines such as triethylamine are particularly preferred.

The copolyestercarbonate of the component (A ') has sufficient impact strength even if its terminal is phenol, but pt-butylphenol, isononylphenol, isooctylphenol, m- or p-. Cumylphenol (preferably p-cumylphenol), chromanyl compounds, such as chroman,
By introducing a bulkier end group, a copolyestercarbonate having a better low temperature impact resistance can be obtained.

Next, the polyester used in the present invention is
Derived from terephthalic acid and cycloaliphatic diols. The cycloaliphatic diol has 6 to 18 carbon atoms. Specific examples include 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like. These alicyclic diols can be used in either the cis or trans configuration, or as a mixture of both. The preferred cycloaliphatic diol is 1,4-cyclohexanedimethanol.

Here, as an optional component, an aliphatic diol can be used in combination with the alicyclic diol. The aliphatic diols have 2 to 18, preferably 2 to 12 carbon atoms. Specifically, ethylene glycol,
1,2-propanediol, 1,3-propanediol,
1,2-butanediol, 2,3-butanediol, 1,3-
Butanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 2,3-propanediol, 1,6-hexanediol, 2-ethylhexanediol-1,3 and the like can be mentioned. . Suitable aliphatic diols are
Ethylene glycol and 1,4-butanediol.

The above-mentioned polyester can be prepared by a known method, for example, US Pat. Nos. 2,465,319, 2,901,466 and 3,047, US Pat.
It can be produced by the method described in No. 539. A preferred polyester is poly (1,4-cyclohexanedimethanol terephthalate) and has the general formula

[0049]

[Chemical 7]

## STR4 ## wherein the cyclohexane ring is selected from the cis and trans isomers thereof.

The preferred range of use of the component (A) and the component (B) is 1 to 90 parts by weight of the component (B) with respect to 99 to 10 parts by weight of the component (A). More preferably, component (B) 5 is added to component (A) 95 to 40 parts by weight.
６０60 parts by weight. The effect of the present invention is not sufficiently exhibited even if the ratio of the component (B) is low or high.

Next, the glass filler used in the present invention has a high refractive index and is preferably closer to polycarbonate. Particularly, those having a refractive index of 1.576 to 1.590 are preferable. Such glass fibers are commercially available from Asahi Fiber Glass Co., Ltd., for example, as ECR glasses. Glass fiber is component (A) 99-4
1 to 60 parts by weight is used with respect to 0 parts by weight. If the amount of the glass filler is too small, sufficient rigidity is not exhibited, and if the amount is too large, the strands are not stable during melt kneading, which is not preferable.

As the form, for example, glass fiber, milled glass, glass beads, glass flakes, glass powder and the like can be used, and these may be used alone or in combination of two or more kinds.

A coupling agent such as aminosilane or epoxysilane can be used to improve the adhesion between the glass filler and the resin. Further, in the case of glass fiber, an epoxy-based or urethane-based binder can be used as a suitable binder.

The difference in refractive index between the component (A ') and the component (C) is 0.01 or less, preferably 0.005.
It is the following. If the difference is larger than 0.01, the transparency of the resin composition is lowered and it becomes impractical.

Since the glass-reinforced polycarbonate resin composition of the present invention has high transparency while maintaining rigidity, it can be advantageously used not only for optical applications such as lenses and prisms, but also because it is lightweight. Sunroof, windows,
It can be used as a substitute for glass in horticultural houses.

[0057]

The present invention will be described in more detail by the following examples. In the examples, the following components were used.

Component (A) (a-1) Polycarbonate (trademark: LEXAN, bisphenol A carbonate, manufactured by Nippon Di-Plastix Co., Ltd., n _D = 1.
582), hereinafter referred to as a PC. Component (A ') CPEC: copolyestercarbonate (n _D = 1.581) prepared as follows; dodecanedioic acid (DDDA) 7.2 g (31 mmol) and NaOH tablets 2.7 g (68 mmol). 180 ml of water
To give a disodium salt of DDDA.

Next, a 2000 ml Molton flask having a sample outlet in the lower part and five ports in the upper part was equipped with a stirring blade, a pH measuring end, an injection tube and a Claisen adapter equipped with a dry ice condenser. 71 g (311 mmol) of bisphenol A, 0.9 ml of triethylamine, 2.0 g (9 mmol) of p-cumylphenol, and 220 methylene chloride were placed in this polymerization flask.
ml and the disodium salt of DDDA prepared above were charged.

Subsequently, phosgene was injected into the flask at a rate of 2 g / min. At this time, 50% NaOH
While adding the aqueous solution through the injection tube, adjust the pH of the solution to 10
Maintained for minutes.

Thereafter, while continuing the injection of phosgene, a 50% aqueous solution of NaOH was added through an injection tube to adjust the pH of the solution to 10.5, and this pH was maintained for 10 minutes.

The total amount of phosgene used was 40 g (4
Was 00 mmol). After the reaction is complete, adjust the pH of the solution to 1
Adjusting from 1 to 11.5, the organic solvent phase was separated from the aqueous phase.

The organic solvent phase was diluted with 300 ml of 2% hydrochloric acid to 3 times.
After washing 5 times with 300 ml of deionized water,
It was dried over anhydrous magnesium sulfate and filtered.

This was put into 1500 ml of methanol to precipitate a polymer. The obtained polymer was separated by filtration, washed once with 500 ml of methanol and then 4 times with 500 ml of ion-exchanged water, and then dried at 110 ° C. for 15 hours.

Thus, a copolyestercarbonate having the structural units of the following formulas (Formula 8) and (Formula 9) in a molar ratio of 90:10 was obtained. Its intrinsic viscosity (measured in methylene chloride at 25 ° C.) was 0.46. Hereinafter, this is abbreviated as CPEC.

[0066]

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[0067]

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Component (B) PCT (manufactured by Eastman Kodak Company): Polyester derived from 1,4-cyclohexanedimethanol and terephthalic acid. General formula (Formula 1
0)

[0069]

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Having a repeating unit represented by: (In Table 1, abbreviated as PCT.)

Component (C) Glass fiber A (trademark: FT121, E glass, refractive index 1.545, manufactured by Asahi Fiber Glass Co., Ltd.) Glass fiber B (trademark: E)
CR glass, refractive index 1.579, manufactured by Asahi Fiber Glass Co., Ltd.

Examples and Comparative Examples The components were mixed in the ratios (weight ratios) shown in Table 1 to obtain 260
Extruded by a twin-screw extruder (30 mm) set to 15 ° C., 150 rpm, 15 Kg / hour (extrusion speed) to form pellets, and then using a molding machine of 80 tons, a cylinder set temperature of 260 ° C. and a mold temperature of 80 Injection molded at ° C.

The haze and flexural modulus of the obtained molded product were measured. The results are shown in Table 1. Haze is 50
The test piece of x50x3 mm was measured using a haze meter, and the flexural modulus was measured according to ASTM D790.

Comparing the examples with the comparative examples, it is clear that by mixing the copolyester according to the invention the transparency is significantly improved and the rigidity is maintained.
As shown in the comparative example, when using a glass of low refractive index,
That is, the effect of the present invention cannot be obtained when the difference in the refractive index with the polycarbonate is large.

[0075]

[0076]

EFFECTS OF THE INVENTION According to the present invention, as described above, a glass-reinforced polycarbonate resin composition that exhibits the transparency peculiar to polycarbonate while maintaining high rigidity can be obtained.

Claims (1)

[Claims] 1. A) 99 to 10 parts by weight of a polycarbonate-based resin and / or polyester carbonate-based resin, B) 1 to 90 parts by weight of a polyester derived from terephthalic acid and an alicyclic diol, and both components A). And B) to a total of 99 to 40 parts by weight, C) 1 to 60 parts by weight of glass filler, and refraction of the component A) polycarbonate-based resin and / or polyester carbonate-based resin and the component C) glass filler. A glass-reinforced polycarbonate resin composition, characterized in that the difference in the ratio is 0.01 or less.